Polymerization of propylene



rf 2,400,520 y.

May21y1946- c.l s. KUHN, JR

- Y POLYMERIZATIN 0F PROPYLENEV FiledvApzfil 2 4, 1944 ArmvNEY l,

Patented May 2l, 1 946 Carl S. Kuhn, Jr., Dallas, Tex.,` assignor, bymesi-1e l f;

assignments. to Socony-Vacuum Incorporated, New York,` N. Y.,

of New York f Application Anri124, 1944, s

soiaims. (ci. 26o-4683.15)

This invention relates ,te the' cataiytie' p1ymerization ofmono-olefins, particularly propylene, and is acontinuation-in-part of'my cependpossible, i, e., co

ing application Serial-Number 403,876, filed July i 24, 1941. Morespecifically, the invention is concerned with Va 'particular typeofpolymerization of mono-oleflns for the simultaneousproduction of anyessentially saturated liquid hydrocarbon product and a highlyunsaturated liquid hydrocarbon product.

In the past mono-olefins wenn utiiizeg'.

Oil Company,` a corporation f yniniv No. 532,489V f miiinationu of the'normal paraffin with the olefin byv an alkylation reaction. Which ofthese reactions is the predominant one depends -uponl the; reactionconditions used; andthe reactiony conditions'l necessary -to favor 'aparticular reactionwill' initurn vary ywith the :particular tration ofthe catalyst, the" temperature vandthe Ahave been polymerized under boththermal and catalytic conditions."

For instance, inthe catalytic operationsysuch catalysts as dilutesulfuric acid, various metallic halides, etc., have been used. Usually`the prod'-v ucts of such reactions have been olefin polymers v whichare linear dimers, trimers, etc., of the original Aolefin reactant. Italso is known that under suitable conditions, certain catalysts, such asconcentrated sulfuric acid and aluminum chloride,

can effect a different type of polymerization of mono-olefins, whereinthere is obtained a top reactantV layer consisting essentially ofsaturated fliquid hydrocarbons and a bottom reactantlayer whichcomprises terpene-like unsaturated hydrof carbons in combination withthe catalyst'. This' latter type of polymerization apparently involves ahydrogen exchangebetween the primary polymerization products resultingin a saturation of one portion of the material at the expense of theother. For this reason the termsK "hydro-polymerization,"dehydropolymerization, and conjunctpolymerization have beenapplied tothis complex reaction to distinguish it from the ordi- Y narypolymerization.Y Therefore, the vconcentration of the acid must besufcient to give con-` junct polymerization, and this lower limit isabout 90%V acid.` For the purposes of defining vmy invention I shallconsider anhydrous hydrogen fluoride as hydrofluoric acid. Accordingly,myl catalyst is one consisting essentially of anhydrous hydrofluoricacid containing'notmore than 10% of water by weight on the basis of theYhydrogen y fluoride content of lthe catalyst although the titratableacidity of the catalyst in the reaction vvzone may be considerablylessthan-90% due to the presence of dissolved hydrocarbonsvand highlyunsaturated polymer product, .which of, course reduce the titratableacidity as well as water.

When an olen is admixedV with Yessentially anhydrous hydrogen .fluorideat least two predominant primary reactions are possible, i. e.,

- addition of hydrogen uoride tothe double bond of the olefin mon'omertoform volatile'alkyl fluorides, and polymerization ofthe olefin monomerand where the reacti -hydrofluoric acid to olefin monomer ratio -exert'with the formationiof they olefin polymers as a primaryl reactionproduct, the essentialconditions will be considered'fromvthe standpointof this reaction, f As `mentioned above, a substantially anhydroushydrofluoric acid isan essentialrre- ',quireme'nt. The ratioofhydrofluoricacid to 'olefin monomer must be high,at all times greaterthan 1 to 1 andpreferably''or 10 to 1 or higher. Ina largescaleoperation, vparticularly on a continuous basis, `the preferred mode of'operationis to'add theolefin monomer to thecatalyst-hydrocarbon mixturewhile agitating' vthe mixture in the manner utilized in -the'presentfdayconventional alkylation processes. l i r The effect of temperaturelvaries widelywith the particular olefinto b'e reacted. In the 'case ofethylene, increasing temperaturesmover the range'of from 15? C.toni-75C. merelyserved toV increase the an'iounty of ethylvuorideformed,

on` rateof ethyleney apalue, the fluorideiwas the preached a reasonablev VA,predominant product: Hydrouoric 'acid-'alone seemed incapable ofsatisfactorily'effecting the polymerization of this olefin.-Withpropylene,

` vthe effectofftemperature on the nature of the reactionlv'vasvery'sharp Invraising'the temperature from '5 C. to -i-l C.,"thereaction-changes l sharply from one of predominantly theformation ofisopropyl. fluoride, 'to fone of almost lentirely polymerization. Theexact temperaturelat which isopropyl fluoride formation; as an `endproduct,

ely eliminated varies aboutl plus or'rninus 5 C. vfrom +l0 C. fwith thehydrofluoric vacid kconcentration and 'acid-olefin monomer ratio.l On

, k the otherhand, with olens of 401' morey carbon atoms, I havenotbeenv able to observe any appreciable formation of ylow-boiling alkyluorides 59 down to low temperatures zat which the reaction rate becomes'slow. "Forfexample at a temperature of 20 C.,polymerization'is-stillthe'major reaction. Polymerization represents thechief reaction vfor propylene as wellas-the'olens of i4 or' more carbonatoms through the ordinary as induced or accelerated bythe catalyticeffect v of o Lthe hydrogen fluoride to the' olefin dimer, trimer,

tetramer, etc. Where `the reaction is carried out in the presence of anormalparamn hydrocarbon.

60 kpreferre solvent a third primary reaction is. theoretically Well asthe moderately elevated temperature levels up to, say,200 C., although'temperatures ,between about +10* and +60 vC. are preferred.

for propylene, and about --20v and Vi60 C; are

d for oleflns of 4 or more carbon atoms.

As mentioned previously, the acid to olen monomer ratio is an importantfactor in securing'V the desired polymerization reaction. Since animportant object of my invention is to secure not only a polymerizationreaction, but to also recover the two types of product, i. e., thesaturated hydrocarbons and the highly unsaturated, terpenelike productssoluble in the catalyst, the relative proportions of acid to totalhydrocarbons in the reaction zone is important. In the absence of inertsolvents an amount of acid of from about up to about 400% by weight ofthe olenic hydrocarbons may be utilized, or expressed in another wayfrom to 500% by weight of olens may be added to the hydrofluoric acidwith separation possible into readily separable layers. Preferably theamount of olefins added is from S31/3% to 200% by weight. Where inertsolvents are utilized, the amount ofV olen which may be added to theacid-hydrocarbon mixture will largel residence time is correlatable withthe reaction ly depend upon the relative proportion of acid and inerthydrocarbon solvent, ,and is normally within the range of from 16%% upto about 200% by Vweight of the amount of acid, with amounts from`25% to150% byA weight preferred. The difference in preferred ranges is dueV tothe fact that the inert solvent does not react to produce largermolecules (which as a result of hydrogen exchange distribute themselvesbetween the acid andhydrocarbon phases) but remains as a distincthydrocarbon phase. Hence, assuming that the amount of solvent is atleast as great as the amount of acid, the minimum amount ofl olefinsnecessarily added, where solvents are employed, is generally reduced byabout one-half to obtain satisfactory conditions of layer separation.Similarly, especially where it is desirable to use relatively largeamounts of inert solvent, the maximum amount of oleiin which may beadded to the catalyst with satisfactory separation after the reactionhas been completed, is reduced.

The process may be carried out, ineither the presence or absence ofsolvents, under conditions, similar to thoseutilized in carrying outalkylation reactions, or the conditions used are what might be termedalkylation conditions with respect to pressure, temperature (within theranges inditemperature and the degree of saturation of the hydrocarbonlayer products desired.

Referring tothe drawing one possible form of carrying out the process ofmy invention is diagrammatically illustrated, which enables thecontinuous production of the conjunct polymer products. According to theform illustrated, the reaction is carried out in the presence of anormal paraffin hydrocarbon solvent. .s

To an emulsion of hydrofluoric acid and an inert solvent such as normalbutane, obtained in the manner hereinafter described, in a coil I inrtemperature control zone 2, an olefin is introduced through line 3provided Ywith a suitable vpump 4.` yThe contact time of the olen chargewith the acid catalyst should be suiiiciently long within Vthetemperature control zone 2. so that a substantial portion of the olefinreacts therein to form the olen dimers, trimers, etc. From coil I, theolefin polymer, solvent-catalyst mixture is led through lines 5 and I toreactor 8 provided with a suitable agitator 9, wherein the emulsion ismaintained for the desired residence time to cated), reaction system,moder of introduction of f reactants and the like. v

Since the reaction gives off a substantial amount of heat, it is usuallydesirable to provide suitable cooling means in order to maintain thetemperature within the preferred limits. Usually the re- Y action willbe carried out so that the hydrogen uoride catalyst is in liquid phase,and, therefore, in such cases'suilicient pressure should be provided tomaintain the catalyst in liquid phase. However, such procedure requiresonly sufficient pressure to maintain the inert solvent, if any, and thehydrogen fluoride inthe liquid state. The olen is then passed throughthe Well-agitated liquid at such a rate that it all reacts to higher---boiling hydrocarbons, wherefore no rise in presf sure results.

Accordingly, relatively low pressures can be used.

Since, in addition to the initial olefin polymerization, I desire toallow hydrogen exchange reactions to occur within the original polymerproducts, further contacting of the reaction mixture with the acidcatalyst is desirable. The amount of residence time, of the hydrocarbonproducts in contact with the catalyst, required to achieve substantialor nearly complete saturation of the acid immiscible hydrocarbons varieswith the reaction conditions and the particular olefin monopermit'thepolymerization reactions to become completed and allow hydrogen exchangeto occur between the olen polymers as previously' described'. Productmixture is continuously withdrawn from the reactor 8, and sent throughline I0 to settling tank I5 wherein the emulsion is allowed to stratifyinto an upper hydrocarbon phase and a lower acid catalyst phase. Fromthe lower portion of the settling tank, catalyst phase is continuouslywithdrawn through line I6, and sent to fractionator I'I, wherein themajor portion of the hydrofluoric acid is distilled oir from the highlyunsaturated terpene-like polymers contained therein. The hydrouoric acidvapors overhead from fractionator II are then sent through line I8 tocondenser I9, collected in receiver 20, and'returned through lines 2|,22 and 23 to reaction coil I. Line 23 is provided with a suitable pump24 to provide the necessary acid circulation.` Make-up hydrofluoric acidis admitted, as necessary, toline 22 through line 25, provided with acontrol valve 2li.A The highly l unsaturated polymer is removed from thebottom of the fractionator I1, and sent through line 30, provided with asuitable pump 3 I, to acid stripper 32." In acid stripper .32, the naltraces of hydro fluoric -acid are removed from the unsaturated polymerproduct by scrubbing the polymer with a hot inert gas such as nitrogenor methane introduced through line 33. This includes not onlyhydrofluoric acidpresent as such, but also hydroe gen fluoridewhich mayhave added to double bonds in.the"unsaturated polymer and isdriven 01Tby moderate heating. The overhead from the stripper 32 is sent tocondenser 34 through line 35, and any condensable material, principallyhydroiiuoricacid, collected in receiver 36, provided witha suitable vent31, and recovered from line 38. Anyhydrogen fluoride escaping with thevent gases may be recovered by any suitable means. The unsaturatedpolymer product is recovered from the bottom of the acid stripperthrough line 39.

. The hydrocarbon phase is withdrawn from the top of settling tank I5,and sent through line 45 to solvent stripper 46. Solvent vapors aretaken shown) through fline y,which will-decomposethe iiuorides,r

Y.the major portion of thehydroiluoric aciddis? rsolvedin'therhydrocarbon layer and mostoLthe readilyy decomposable organiciluorides, which fare'V removed `from the'hydrocarbons fculated throughline 18| by line 63, provided withy A der withdrawn through valvedylinel 18.

this 'kerosene Vboiling -of jcolumnthroughV y nantly saturatedlhydrocarbon material and can be further fractionated -Vunder vacuum'ifYneceson overhead,- sent to a'lsuitable condenser (not I1, collectedinla. receiver (not shown).fandv returned lthrough line, .provided with asuitable pump, to line 23, wherein ,the solventis emulsiiied `with the.hydroiluoric acid'r'ecycle Vreturning vthroughline 22,` and returned toreaction coil l. IA line 50 is provided, connectingj'linesjl,and 1., andcontrol valves 5I rand 52 are provided in lines'50 and", respec-,tively,so that any y desired portion f'tiierecycle solventI maybereturned only to reactor 8,rather than beingv emulsified with the acidrecycle and sentv through' reaction coil l. The bottomsfrom the solventstripper are withdrawn through line 55, and sentto heating'coil 58'in'asuitable'heater 51, Whreinthey are preheated toa temperature 'Althoughmaybe formed in small ramounts'in 'the reaction,

fluoric acid'in the solvent stripper andereturned iscountercurscrubber58, wherein the liquid alkali solution.

rently" scrubbed with an' aqueous yThe scrubbing solution isremoved fromthe bottom of the Yscrubber through line 60, and recirmeans of-/pump`82. Thescrubbing solutionmay scrubbing'medium supplied "to line 8|through o v a suitablecontrol valve 64. .The scrubbed hydrocarbon liquidis removed line 18, provided witha pump 11, tothe upper portion ofthecolumn asreiiux and the remain- This material consists of substantiallysaturated hydrocarbons'boiling ini the gasoline range. vVapors y Y lwithdrawnl from the'center'of thecolumn through line 80,'con`densed incondenser 8|, and collected in receiver 82,'are largelykerosene boilingrange saturated hydrocarbons and are drawn. oi for recovery throughgvalved line` 83. 'A "portion-Tof ymaterial may bef-returned Vto thecolumn through line 84, by meansofspump.; r ..8-5, asrefiux. Thematerialcoming oi! the-bottom line 88 is a 'heavypredomiv.

rial.

- {Manymodications'fof the process illustrated Y' l65 will 'be readilyapparent"to-`those skilledin 'the solventv is used, that it should notcontain any 'large amountof isoparaillns, especiallythe lightisoparafdns, isobutane and isopentane. Were apbe withdrawn in part ycontinuously, or from rvtime totime, andfresh product mixture t0 tionalcontacting atthe -20 Hmeanthat all or part ashydro- Vto the'reactionzone, some 'hydrofluoricacid vor v yhydroiiuoric Aacid forming compoundsremain in V25 fof' polymerization) preciable amounts ofv lightisoparamns present with the hydrouoric acidat the point o olefin monomerintroduction. alkylation would set in `as a 'competingfreactiom For thisreason.. as discussed herein,:inert'solvents such as the normal paraiiinare used. In continuousoperation, this produces a distinctioninthepreferredmode of operation over that utilized inthe'conventionalcontinuous alkylationprocess. Sincefthe saturated productformed from theyolefin polymers contains branched chain hydrocarbons. (the l natureof-which depending upon the particular olefin being processed) Ikprefernot to recirculate the the point of olen introduction' in order to avoidalkylation of isoparafiini'c polymer products. One way of accomplishingthis is shown' in the drawing, wherein the initialolen addition .is toproduct-free acid, and the addilonger residence time is reactor. .1 Thisdoes 'znot kof the product,..mixture could not be recirculated and theolefin introe'iiected .in a separateV "duced into the product-acidemulsion, since any i' alkylation that occurs Adoes no harm, but merelyincreases the amount of `heavier saturated hydrocarbons formed. `:Also,rthe isoparaiiins initially formed are largelythose of. six or morecarbon y atoms (depending .uponthe olen 'andthejextent 4`For the purposeof Afurtherillustrating'the'invention,"the following examplesv aregiven'forjthe `conjuncttpolymeriz'ation of propylen'e, it is 'to beunderstood that'theinvention is not tobellmited rby the'speciflc detailsthereof as ktherev'maybe V'variations therefrom scope ofthe invention.

*A v(agitatei'if anhydrous riod of145 minutes.

without departing y from the o' 6,32'partsfof'propylene v(5%'propane) by.Weight were added'to QlO'parts `byweight of thoroughly l hydrogeniluoride over ape- `"The temperature of theI reaction mixture wasmaintained at,20'C., plus or minus 315C. 'A After completing theAaddition of propyleney 291 parts by weight -of;normal v butane wereadded. Agitation was discontinued, v.and

. two liquid phases, i. e., the saturated hydrocarbon phase-and theunsaturated hydrocarbon-hy- ;'drofluoricfacid phase allowed to separate.1 The muy distilled from v.two lphases were then'separately recoveredand the hydroiiuoricv acid and normal butane carethe acid andhydrocarbon layers. The amount of Cs plus saturated hydrocarbonsemthejtep or 65.9%by weight y Ysaryvto produce alvaluabl'e lubricatingyoilmatej l Y Acosityjof 3l1fseconds, ya 210 YF. viscosity'of49.9

Afromthe lower-.layer was .34.4% of the f propylenecharged; v

layer was396 parts by Weight, "of the -propy'lene charged, vwhile` theamount of polymer products recovered 207parts.by'weight, or

Y The distribution. ofjthe .hydrocarbons `formingthe` saturated Weightlperf Tnematriai disnuingabove 185 amic mm. of.mercurytipressure'had a100 'F. Saybolt vis- '.secondS., and aviscosity index vof 65:- Its 'pourpoint was -v-40*" .and itsj'Conrads'on carbon residuewas 0.04%, v f yExample 2 Weight per Boiling pt., C. cent of total product 25-2o0 o. at76o mm V ,v f 25.8 200 C. at i60-185 C. at l0 mln 67. 6 185 C.+ at 10mul 6. 6

Example 3 To a well'agitated mixture of 297 parts of anhydrous hydrogenfluoride and 780 parts of normal butane by weight, 117 parts ofpropylene (5% propane) by weight were added over a period of 177minutes. The temperature of the reaction mixture was maintained at 20C., plus or minus 3 C. After completing the addition o f propylene,agitation was discontinued, and the two liquid phases, i. e.; thesaturated hydrocarbon phase j and the unsaturatedhydrocarbon-hydroiluoric acid phase allowed to separate The two phaseswere then separately recovered and the hydrofiuoric acid and normalbutane carefully distilled from the acid and the hydrocarbon layers. Theweight of Cs-l-saturated hydrocarbons in the top layer was 72.5 parts byweight, or 65.3% by weight of the propylene charged, while the weight ofpolymer products recovered from the lower layer was 29.0 parts by weightor 26.1% of the propylene charged. The distribution of the hydrocarbonsforming the saturated hydrocarbon product was as follows:

' Wt. percent A of total 25200 C; at 760 mm 40.3 Above 200 C, at r160 mm59.7

All of the normal butane was recovered, and there l was no evidence ofany having reacted with the propylene.

These three examples also illustratethe marked tenes, etc., and isfurther exemplied in my copending application Serial llumber't' 32,490nled April 24, 1944, covering the conjunct polymerizai tion ofV oleiinsof four or more carbon atoms.

An increase in the temperature from to 50 C., when operating in -theabsence of a solvent in Example 2, produced a 270 percent increase inthe gasoline boiling range material and an even more marked decrease inthe lubricating oil range material. Obviously, therefore, if itisdesired to produce primarily the gasoline range material the processwould be operated at elevated temperatures (above 20 C.) in the presenceof a solvent, Whereasif lubricating oil range material is desired theprocess would be. conducted in the absence of a solvent at relativelylow temperatures, e. g., from 10 to 20 C.

Since the reaction product in the acid layer is composed of a verysubstantial portion of-terpene-like hydrocarbons, it can be appreciatedreadily that efilcient recovery of such fraction is necessary for anypractical operation. Accordingly, from the above examples, it can beseen that my process permits efllcient recovery of all the reactionproduct, whereas prior art processes have failed to doso and because ofthis failure have received little attention.

The terpene-like unsaturated hydrocarbons form -a valuable producthaving many potential uses, primarily as. a raw material for themanufacture of other products. Thus, for example, this product maybesteam-distilled to yield a suitable fraction that may serve as aturpentine still. further, they may substitute, or other solvent-typematerial, or the product or fraction thereof may be hydrogenated; as,for example, the non-steam-distillable residue (or vacuumfdistillationresidue which may be considered as, an equivalent) may be hydrogenatedto form material boiling in the lubricating oil range; Further,hydrocarbons of this product may be hydrogenated to aromatics, or, bereacted with a suitable resinifying agent'to form desirable resins.

'Many modifications of my invention will be apparent to those skilledfore only suchlimitations should be imposed as are indicated in theappended claims.

1. The process for the conjunct polymerization of propylene rto producesaturated hydrocarbon polymersv and terpene-likel unsaturatedhydrocarbons which comprises contacting the mono-olefin eiect oftemperature and solvent ratio on the composition of the saturatedhydrocarbon product. Thus, ample 1 with that from Example', both'ofwhich were carried out at 20 C., it will be seen that the presence ofthe solvent (normal butane) increased the amount of material boilingy inthe gasoline range by over 400 percent. Increasing the amount of inertsolventnot only' increases the amount of gasoline boiling hydrocarbonsin the hydrocarbon layer, but also increases the relative amount of lowmolecular Weight hydrocarbons of highly unsaturated character in theacid layer. Accordingly by theuse of inert solvent and by varying therelative proportions of inertsolvent to olefin utilized, the proportionof low -by comparing the product from Ex- .tween the, vpropylene with acatalyst consisting essentially of hydroiluoric acid of. about'90'to 1007b concentration,

' correlating the amount of hydroiluoric'acid, the -reaction temperatureand `time to effect polymerization of propylene as the principalreactionof the process andAV allowhydrogen exchange bey 'polymers to occurto'form saturated hydrocarbon material anda, highly unsaturatedhydrocarbon material,` separating the vbons from the'acid phase.'

reaction mixture into an acid phase and a hydrocarbon phase, recoveringsaturated hydrocarbons heavier, than propane from the hydrocarbon phase,V and terpene-like unsaturated `hydrocar- 2. A process for thepolymerization of propylene which comprises addingH from about 16% toabout 500 parts of propylene to about 100. parts by weight ofessentially kanhydrous -hydrofluoric acid. as a. catalyticv agent at atemperature of from about +10 C.A to about+200 C. at a, rate to highmolecular weight hydrocarbon products Y may be controlled.l Thisconsideration is general for the various olens, propylene, butenes,pen-y such that the relative proportion by weight of propylene monomerin the reaction mixture isY less than that of the hydrofluoric acid,agitating in the art, and there-` the resulting mixture for a period oftime sufficient to allow the saturation of a considerable proportion ofthe propylene polymers to occur, separating the hydrocarbon phasecontaining the saturated hydrocarbons from the acid catalyst phasecontaining highly unsaturated polymer material, and separatelyrecovering the hydrocarbons from each of said phases.

3. A process for the polymerization of propylene which comprises addingfrom about 162/3 to about 500 parts of propylene to about 100 parts byweight of essentially anhydrous hydrouoric acid as a catalytic agentfrom about +10 C. to 60 the relative proportion by weight of propylenemonomerin the reaction mixture is less than that of the hydrofiuoricacid,`agitating the resulting mixture for from about 30 minutes to about180 minutes to allow saturation of a considerable portion of thepropylene polymers to ocour, separating the hydrocarbon phase containingthe saturated hydrocarbons from the acid catalyst phase containinghighly unsaturated polymer material, and separately recovering thehydrocarbons from each of said phases.

4. A process for the polymerization of propylene which comprisesadding'from about 162/3 to about 200 partsy of propylene to a mixture ofabout 100 parts by Weight of essentially anhydrous Yhydroiiuoric acidand at least as much of a normal paraiiin hydrocarbon as acid at atemperature of from about -|-l C. to about +60 C. at a rate such thatthe ratio of acid to propylene monomer is at least to 1, allowing thehydrocarbons to remain in contact with the acid catalystfor a. residencetime suilicient to effect polymerization of propylene a's the principalreaction of the process and allow hydrogen exchange between the primarypolymers to occur to form saturated hydrocarbon material and a highlyunsaturated hydrocarbon material, separating the reaction mixture intoan acid phase and a hydrocarbon phase, recovering saturated hydrocarbonsheavier than propane from the hydrocarbon phase, and terpene-likeunsaturated hydrocarbons from the acid phase.

5. In a process for the polymerization of propylene to produce saturatedhydrocarbons and terpene-like unsaturated hydrocarbons the steps of (1)introducing the propylene monomer into t a liquid mixture of a normalparafn hydrocarbon and hydrofluoric acid maintained at a ternperatureofv between about and 200 C. at a rate such that the amount of propylenemonomer by weight at any time is less than one-tenth the amount ofhydroi'luorio `acid, (2) transferring the mixture of primaryypolymerization products and acid catalyst to a reaction zone whereinthe mixture is agitated and maintained at a temperature of between about10 and 200 C. and allowing further contactingof the acid catalyst andpropylene including primary polymerization products to occur during aresidence time sufcient to allow substantial saturation of acidimmiscible propylene polymers, (3) withdrawing reaction mixturecontaining `hydrofluoric acid and hydrocarbons including propylenereaction products and any unreacted propylene monomer from said reactionzone, (4) passing the mixture so Withdrawn to a separation zone for`separation into a lower acid phase and an upper hydrocarat atemperature of C. ata rate such that y 5 vaporizing hydrofluoric acidfrom the terpenelike unsaturated hydrocarbons therein, (6) condensingand' returning at least part of the hydrofluoric acid to the point ofsaid propylene introduction, and (7) withdrawing the hydrocarbon phaseand recovering predominantly Vsatu rated C5 plus hydrocarbon producttherefrom. l 6. In a process for the polymerization of propylene toproduce saturated hydrocarbons and terpene-like unsaturated hydrocarbonsthe steps of (1) introducing the propylene monomer into a liquidmixture'of a normal parailin hydrocarb on and h'ydrcfluoric acid maintained ata temperature of between about 10 and 60 C. at a rate such that theamount of Apropylene monomer by weight at any time yis less thanone-tenth the amount of hydroiiuoric acid, (2) transferring the mixtureof primary polymerization products and acid catalyst to a reaction zonewherein the mixture is agitated and maintained at a temperature ofbetween about 10 C. and 60 C, for

a residence time of from to 180 minutes, (3)

bon phase, (5) withdrawing thel acid phase and withdrawing reactionmixture containing hydroi'luoric acid and hydrocarbons includingpropylene reaction products and any unreacted propylene monomer fromsaid reaction zone, (4) passing the mixture so withdrawn to a separationzone for `separation into a lower acid phase and an upper hydrocarbonphase, (5) Withdrawing the acid phase and vaporizing hydroiiuoric acidAfrom theterpene-like unsaturated hydrocarbons therein, (6) condensingand returning at least part oi' the hydrofluoric acid to the point ofsaid propylene introduction, and ('1) withdrawing the hydrocarbon phaseand lrecovering predominantly saturated Cs vrplus-hydrocarbon productstherefrom. c

7. A process for the conjunct polymerization of propylene to producesaturated hydrocarbon polymers and terpene-like unsaturated hydrocarbonswhich comprises contacting the propylene in admixture with a solvent forsaturated hydrocarbons With a catalyst consisting essentially ofhydrofluoric acid of about to 100 percent concentration at a temperatureof from about 10 C. to v200" C., separating the reaction mixture intotwo phases, recovering the hydrocarbon phase containing the saturatedhydrocarbon poly/mers, vaporizing the hydrofluoric acid from thecatalyst phase and recovering the terpene-like .unsaturated hydrocarbonsremaining after removal of the hydrofluoric acid.

8. A process for the production of paraflinic hydrocarbons frompropylene which comprises adding about 16% of propyleneto a mixtureessentially consisting of about parts of essentially anhydrous hy.-drfluoricacid as a catalytic agent and atleast an equal amount of anormal parain at a temperature between` about 10 and labout 200 C.

at a rate such that the relativeproportionby weight of propylene in themixture is less than that of the hydrouoric acid to eiect polymerizationof the propylene, agitating the resulting mixture for a period of timesuiiicient to allow saturationof a major proportion of the polymerproducts to occurto form acid immiscible parafnic hydrocarbonstherefrom, separating and recovering the parafiinic hydrocarbon productsfrom the acid catalyst.

' CARL S. KUHN,4 JR.

to about 200 parts by weight

